Arctic observations of hydroperoxymethyl thioformate (HPMTF) – seasonal behavior and relationship to other oxidation products of dimethyl sulfide at the Zeppelin Observatory, Svalbard

Abstract

Abstract. Dimethyl sulfide (DMS), a gas produced by phytoplankton, is the largest source of atmospheric sulfur over marine areas. DMS undergoes oxidation in the atmosphere to form a range of oxidation products, out of which sulfuric acid (SA) is well known for participating in the formation and growth of atmospheric aerosol particles, and the same is also presumed for methanesulfonic acid (MSA). Recently, a new oxidation product of DMS, hydroperoxymethyl thioformate (HPMTF), was discovered and later also measured in the atmosphere. Little is still known about the fate of this compound and its potential to partition into the particle phase. In this study, we present a full year (2020) of concurrent gas- and particle-phase observations of HPMTF, MSA, SA and other DMS oxidation products at the Zeppelin Observatory (Ny-Ålesund, Svalbard) located in the Arctic. This is the first time HPMTF has been measured in Svalbard and attempted to be observed in atmospheric particles. The results show that gas-phase HPMTF concentrations largely follow the same pattern as MSA during the sunlit months (April–September), indicating production of HPMTF around Svalbard. However, HPMTF was not observed in significant amounts in the particle phase, despite high gas-phase levels. Particulate MSA and SA were observed during the sunlit months, although the highest median levels of particulate SA were measured in February, coinciding with the highest gaseous SA levels with assumed anthropogenic origin. We further show that gas- and particle-phase MSA and SA are coupled in May–July, whereas HPMTF lies outside of this correlation due to the low particulate concentrations. These results provide more information about the relationship between HPMTF and other DMS oxidation products, in a part of the world where these have not been explored yet, and about HPMTF's ability to contribute to particle growth and cloud formation.

Impact of Biomass Burning on Arctic Aerosol Composition

“…Despite the similar values for the O:C ratio and numC between BB aerosol and the rest of the year, respectively, the BB aerosol shows less variation for each of these three properties. The higher variation in the rest of the year could reflect the different source contributions to the organic aerosol, such as an increased contribution of marine aerosols, i.e., methanesulfonic acid (CH 4 O 3 S), which has a high O:C ratio and is prevalent in May and June . Moschos et al reported O:C ratios from two years (2017–2018) of offline Arctic filter samples analyzed with an aerosol mass spectrometer (AMS) and positive matrix factorization (PMF) that are overall lower (approximately 0.2 to 0.8), although they also show a large spread during the year, similar to our results.…”

“…The particle inlet of the FIGAERO–CIMS was connected to the whole air inlet via stainless steel tubing (length: approximately 6 m, 4 LPM sampling flow). For more details on the FIGAERO–CIMS operation see Gramlich et al 36 and Siegel et al 37 …”

“…The particle inlet of the FIGAERO−CIMS was connected to the whole air inlet via stainless steel tubing (length: approximately 6 m, 4 LPM sampling flow). For more details on the FIGAERO−CIMS operation see Gramlich et al 36 and Siegel et al 37 The FIGAERO−CIMS data were processed using Tofware 38 (Aerodyne Research Inc.). The data were acquired at 1 s time resolution until mid February, thereafter at 2 s. For the analysis, data were averaged to a time resolution of 30 s. The ions detected by the CIMS were attributed their molecularlevel chemical composition by using a peak-fitting algorithm provided by Tofware V3.2.0.…”